JP2006139213A - Near infrared ray absorbing filter for plasma display and display using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near infrared ray absorbing filter for a plasma display having absorption in a wide near infrared ray region, high durability and transmittance for visible rays, and also to provide a plasma display. <P>SOLUTION: The near infrared ray absorbing filter for a plasma display contains at least three kinds in the following four kinds of phthalocyanine compounds A to D in a transparent resin. The compounds are: a compound (A) expressed by the formula [I], wherein at least four in A<SP>1</SP>to A<SP>16</SP>contain sulfur atoms and chlorine atoms, and M<SP>1</SP>represents vanadium oxide; a compound (B) expressed by the formula [I], wherein at least four in A<SP>1</SP>to A<SP>16</SP>contain sulfur atoms but no chlorine atom, and M<SP>1</SP>represents vanadium oxide; a compound (C) expressed by the formula [I], wherein at least four in A<SP>1</SP>to A<SP>16</SP>contain nitrogen atoms but no sulfur atom, and M<SP>1</SP>represents vanadium oxide; and a compound (D) expressed by the formula [I], wherein at least four in A<SP>1</SP>to A<SP>16</SP>contains nitrogen atoms but no sulfur atom, and M<SP>1</SP>represents copper. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a near-infrared absorption filter for plasma display having near-infrared absorptivity. The present invention also relates to a plasma display provided with such a filter.

  It is said that electromagnetic waves generated by electrical or electronic devices may adversely affect other devices and may affect human bodies and animals. As an example, an electromagnetic wave with a frequency of 30 MHz to 130 MHz is generated from a plasma display (hereinafter may be abbreviated as PDP), which may affect surrounding computers or computer-utilized equipment. It is desired that the electromagnetic wave to be transmitted is not leaked to the outside as much as possible.

  The PDP also uses a mixed gas of neon and xenon as the discharge gas, so it emits near infrared light with a wavelength of 800 nm to 1000 nm. This near infrared light is used for various devices using the near infrared light, for example, remote home appliances. It is said that there is a possibility of causing malfunction of communication devices using near infrared rays such as controllers, personal computers and cordless phones, and improvement is also desired in this respect.

  Conventionally, as an improvement of the above, there is one that forms a transparent resin film containing a near-infrared absorbing dye on a transparent substrate film, but the near-infrared absorbing dye absorbs in a wide near-infrared region. In many cases, onium dyes such as diimmonium and aminium dyes are used for the reason. However, since onium dyes are deactivated and discolored in a resin having a reactive group, it is difficult to mix them with an adhesive or a dry laminating agent (see, for example, JP-A-10-180922).

  On the other hand, metal complex dyes such as phthalocyanine dyes and dithiols are known as near infrared absorbing dyes that are stable among resins having reactive groups.

  Although phthalocyanine dyes are stable among resins having a reactive group, conventionally known ones absorb at 700 to 900 nm, and are combined with dyes having absorption in a wavelength region longer than 900 nm, such as the above diimonium dyes. Was almost. In addition, the absorption wavelength range of conventional phthalocyanine dyes is not necessarily optimal, and the absorption range is narrow due to the molecular structure. Therefore, near infrared absorption ability is realized in a wide wavelength range if multiple types of phthalocyanine dyes are not used. I can't. In order to give appropriate absorption in a wide near-infrared region, several kinds of dyes must be used, and there is a problem that the visible light transmittance is lowered.

On the other hand, metal complexes such as dithiols are stable among resins having reactive groups and some have absorption in a relatively wide near-infrared region, but have low solubility and have problems with usability (for example, Japanese Patent Application Laid-Open No. 2004-2004). -29436).
JP-A-10-180922 JP 2004-29436 A

As described above, as far as the present inventors know, near-infrared absorbing materials using conventional phthalocyanine dyes have both durability, wide-ranging near-infrared absorption, and transmittance in the visible light region. It has not been.
An object of the present invention is to provide a near-infrared absorption filter that uses a phthalocyanine dye and is stable even in a resin having a reactive group, has absorption in a wide near-infrared region, and has a relatively high visible light transmittance. is there. Furthermore, another object of the present invention is to provide a plasma display to which the near-infrared absorption filter is applied after the above-described problems are solved.

As a result of intensive studies in view of the above-mentioned problems, the present inventors have used three or more phthalocyanine dyes having a specific structure, so that they are stable even in a resin having a reactive group, have absorption in a wide near infrared region, The inventors have found that a near-infrared absorbing film having a high visible light transmittance can be obtained, and have completed the present invention.
The first invention relates to a near-infrared absorbing filter for plasma display, characterized in that the transparent resin contains at least three of the following four types of phthalocyanine compounds (A) to (D). .

（式〔Ｉ〕中、Ａ^１〜Ａ^１６は、各々独立に、水素原子、ハロゲン原子、水酸基、アミノ基、ヒドロキシスルホニル基、アミノスルホニル基、あるいは窒素原子、硫黄原子、酸素原子またはハロゲン原子を含んでも良い炭素数１〜２０の置換基を表し、かつ、隣り合う２個の置換基が連結基を介して繋がっていてもよい。Ｍ^１は、酸化バナジウムまたは銅を表す。）
第２の発明は、第１に発明において、前記透明樹脂が、アクリル、ポリエステル、ウレタン樹脂成分を少なくとも１種以上含む近赤外線吸収フィルタに関するものである。 Phthalocyanine compound (A):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are substituents via a sulfur atom, and at least three have a chlorine atom. M ¹ is oxidized) Vanadium.)
Phthalocyanine compound (B):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are substituents via a sulfur atom and substantially have no chlorine atom. M ¹ is Vanadium oxide.)
Phthalocyanine compound (C):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are a substituent via a nitrogen atom and substantially free of a substituent via a sulfur atom). M ¹ is vanadium oxide.)
Phthalocyanine compound (D):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are a substituent via a nitrogen atom and are substantially free of a substituent via a sulfur atom. ¹ is copper.)

(In the formula [I], A ^{1 to} A ¹⁶ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydroxysulfonyl group, an aminosulfonyl group, a nitrogen atom, a sulfur atom, an oxygen atom, or a halogen atom. It represents a substituent having 1 to 20 carbon atoms which may be contained, and two adjacent substituents may be connected via a linking group, and M ¹ represents vanadium oxide or copper.
A second invention relates to a near-infrared absorbing filter according to the first invention, wherein the transparent resin contains at least one acrylic, polyester, or urethane resin component.

  A third invention relates to a plasma display according to the first or second invention, wherein a near-infrared absorption filter is disposed on the viewing side of the display.

  According to the first invention, since three or more kinds of phthalocyanine dyes having a specific structure are used as the near-infrared absorbing dye in the near-infrared absorbing film, it is stable even in a resin having a reactive group and has absorption in a wide near-infrared region, There is an effect that a near-infrared absorption filter having a relatively high visible light transmittance can be obtained.

  According to the second invention, in addition to the effects of the first invention, as a transparent resin containing a near infrared absorbing dye, a resin containing at least one acrylic, polyester, or urethane resin component is used. There is an effect that an adhesive or a dry laminating agent having infrared absorptivity can be obtained.

  According to the third invention, it is possible to provide a display in which a near-infrared absorption filter capable of exhibiting the effects of the first or second invention is laminated on the front surface.

<Near-infrared absorbing filter>
The near-infrared absorbing filter for plasma display according to the present invention is characterized in that the transparent resin contains at least three of the following four types of phthalocyanine compounds (A) to (D).

（式〔Ｉ〕中、Ａ^１〜Ａ^１６は、各々独立に、水素原子、ハロゲン原子、水酸基、アミノ基、ヒドロキシスルホニル基、アミノスルホニル基、あるいは窒素原子、硫黄原子、酸素原子またはハロゲン原子を含んでも良い炭素数１〜２０の置換基を表し、かつ、隣り合う２個の置換基が連結基を介して繋がっていてもよい。Ｍ^１は、酸化バナジウムまたは銅を表す。）
フタロシアニン化合物（Ａ）〜（Ｄ）
本発明におけるフタロシアニン化合物（Ａ）〜（Ｄ）は、上記式〔Ｉ〕で表される化合物において、置換基Ａ^１〜Ａ^１６ならびにＭ^１に関する所定の条件が満たされる限りにおいて特に制限を受けないが、以下に具体的に記載する。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、沃素原子が挙げられる。この中では、特にフッ素原子および塩素原子が好ましい。 Phthalocyanine compound (A):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are substituents via a sulfur atom, and at least three have a chlorine atom. M ¹ is oxidized) Vanadium.)
Phthalocyanine compound (B):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are substituents via a sulfur atom and substantially have no chlorine atom. M ¹ is Vanadium oxide.)
Phthalocyanine compound (C):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are a substituent via a nitrogen atom and substantially free of a substituent via a sulfur atom). M ¹ is vanadium oxide.)
Phthalocyanine compound (D):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are a substituent via a nitrogen atom and are substantially free of a substituent via a sulfur atom. ¹ is copper.)

(In the formula [I], A ^{1 to} A ¹⁶ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydroxysulfonyl group, an aminosulfonyl group, a nitrogen atom, a sulfur atom, an oxygen atom, or a halogen atom. It represents a substituent having 1 to 20 carbon atoms which may be contained, and two adjacent substituents may be connected via a linking group, and M ¹ represents vanadium oxide or copper.
Phthalocyanine compounds (A) to (D)
The phthalocyanine compounds (A) to (D) in the present invention are not particularly limited as long as the predetermined conditions regarding the substituents A ^{1 to} A ¹⁶ and M ¹ are satisfied in the compound represented by the formula [I]. Is specifically described below.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom and a chlorine atom are particularly preferable.

Examples of the substituent having 1 to 20 carbon atoms that may contain a nitrogen atom, a sulfur atom, an oxygen atom, or a halogen atom include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso-butyl group. Linear, branched or cyclic alkyl such as a group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, etc. Group, methoxymethyl group, phenoxymethyl group, diethylaminomethyl group, phenylthiomethyl group, benzyl group, p-chlorobenzyl group, p-methoxybenzyl group, etc. -Aryl groups such as methoxyphenyl group, pt-butylphenyl group, p-chlorophenyl group,
Methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, Cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, alkoxy group such as 2-ethylhexyloxy group, alkoxyalkoxy group such as methoxyethoxy group and phenoxyethoxy group, hydroxyalkoxy group such as hydroxyethoxy group, benzyloxy Group, aralkyloxy group such as p-chlorobenzyloxy group, p-methoxybenzyloxy group, phenoxy group, p-methoxyphenoxy group, pt-butylphenoxy group, p-chlorophenoxy group, o-aminophenoxy group, p-diethylaminoph Phenoxy aryloxy group such as a group,
Acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, n-butylcarbonyloxy group, iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group Alkylcarbonyloxy groups such as n-pentylcarbonyloxy group, n-hexylcarbonyloxy group, cyclohexylcarbonyloxy group, n-heptylcarbonyloxy group, 3-heptylcarbonyloxy group, n-octylcarbonyloxy group, benzoyloxy group P-chlorobenzoyloxy group, p-methoxybenzoyloxy group, p-ethoxybenzoyloxy group, pt-butylbenzoyloxy group, p-trifluoromethylbenzoyloxy group, m-trifluoro B methylbenzoyl group, o--aminobenzoyl group, p- diethylamino benzoyloxy arylcarbonyloxy group such as a group,
Methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, t-butylthio group, n-pentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group, alkylthio group such as 2-ethylhexylthio group, benzylthio group, p-chlorobenzylthio group, aralkylthio group such as p-methoxybenzylthio group, phenylthio group, p-methoxyphenylthio Group, pt-butylphenylthio group, p-chlorophenylthio group, o-aminophenylthio group, o- (n-octylamino) phenylthio group, o- (benzylamino) phenylthio group, o- (methylamino) Phenylthio group, p-diethylaminophenylthio group, Chiruchio arylthio group such as a group,
Methylamino group, ethylamino group, n-propylamino group, n-butylamino group, sec-butylamino group, n-pentylamino group, n-hexylamino group, n-heptylamino group, n-octylamino group, 2-ethylhexylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, di-n-butylamino group, di-sec-butylamino group, di-n-pentylamino group, di-n-hexyl Alkyl group such as amino group, di-n-heptylamino group, di-n-octylamino group, phenylamino group, p-methylphenylamino group, pt-butylphenylamino group, diphenylamino group, di- arylamino groups such as p-methylphenylamino group, di-pt-butylphenylamino group, acetylamino group, ethyl Nylamino group, n-propylcarbonylamino group, iso-propylcarbonylamino group, n-butylcarbonylamino group, iso-butylcarbonylamino group, sec-butylcarbonylamino group, t-butylcarbonylamino group, n-pentylcarbonylamino Group, n-hexylcarbonylamino group, cyclohexylcarbonylamino group, n-heptylcarbonylamino group, 3-heptylcarbonylamino group, n-octylcarbonylamino group and other alkylcarbonylamino groups, benzoylamino group, p-chlorobenzoylamino Group, p-methoxybenzoylamino group, p-methoxybenzoylamino group, p-t-butylbenzoylamino group, p-chlorobenzoylamino group, p-trifluoromethylbenzoylamino group, m-trif Oro methylbenzoyl arylcarbonylamino group such as an amino group,
Hydroxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butyloxycarbonyl group, iso-butyloxycarbonyl group, sec-butyloxycarbonyl group, t-butyl Alkoxycarbonyl groups such as oxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, methoxy Alkoxyalkoxycarbonyl groups such as ethoxycarbonyl group, phenoxyethoxycarbonyl group, hydroxyethoxycarbonyl group, benzyloxycarbonyl group, phenoxycarboni Group, p- methoxyphenoxy group, p-t-butyl phenoxy carbonyl group, p- chlorophenoxy carbonyl group, o- aminophenoxy group, p- diethylamino phenoxycarbonyl aryloxycarbonyl groups such as,
Aminocarbonyl group, methylaminocarbonyl group, ethylaminocarbonyl group, n-propylaminocarbonyl group, n-butylaminocarbonyl group, sec-butylaminocarbonyl group, n-pentylaminocarbonyl group, n-hexylaminocarbonyl group, n -Heptylaminocarbonyl group, n-octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl group, di-n-propylaminocarbonyl group, di-n-butylaminocarbonyl group, di-sec Alkylaminocarbonyl such as -butylaminocarbonyl group, di-n-pentylaminocarbonyl group, di-n-hexylaminocarbonyl group, di-n-heptylaminocarbonyl group, di-n-octylaminocarbonyl group Group, phenylaminocarbonyl group, p-methylphenylaminocarbonyl group, pt-butylphenylaminocarbonyl group, diphenylaminocarbonyl group, di-p-methylphenylaminocarbonyl group, di-pt-butylphenylaminocarbonyl Arylaminocarbonyl groups such as groups,
Methylaminosulfonyl group, ethylaminosulfonyl group, n-propylaminosulfonyl group, n-butylaminosulfonyl group, sec-butylaminosulfonyl group, n-pentylaminosulfonyl group, n-hexylaminosulfonyl group, n-heptylaminosulfonyl Group, n-octylaminosulfonyl group, 2-ethylhexylaminosulfonyl group, dimethylaminosulfonyl group, diethylaminosulfonyl group, di-n-propylaminosulfonyl group, di-n-butylaminosulfonyl group, di-sec-butylaminosulfonyl group Group, alkylaminosulfonyl group such as di-n-pentylaminosulfonyl group, di-n-hexylaminosulfonyl group, di-n-heptylaminosulfonyl group, di-n-octylaminosulfonyl group, phenylamino Aryl such as sulfonyl group, p-methylphenylaminosulfonyl group, pt-butylphenylaminosulfonyl group, diphenylaminosulfonyl group, di-p-methylphenylaminosulfonyl group, di-pt-butylphenylaminosulfonyl group An aminosulfonyl group etc. are mentioned.

Examples of the substituent that two adjacent substituents may be linked via a linking group include a substituent that forms a 5-membered ring or a 6-membered ring via a heteroatom represented by the following formula or the like. Can be mentioned.

The “substituent through sulfur atom” in the phthalocyanine compounds (A) and (B), or the “substituent through nitrogen atom” in the phthalocyanine compounds (C) and (D) includes an amino group, an aminosulfonyl group, Examples thereof include an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, an alkylcarbonylamino group, and an arylcarbonylamino group. The absorption wavelength of phthalocyanine is usually about 600 to 750 nm. However, when a substituent via a sulfur atom or a nitrogen atom is introduced, the absorption becomes longer, and the absorption reaches 800 nm or more. To that end, at least four of A ^{1 to} A ¹⁶ are a substituent via a sulfur atom and / or a substituent via a nitrogen atom, more preferably eight or more are a substituent via a sulfur atom and / or It is a substituent through a nitrogen atom.

The near-infrared absorption filter according to the present invention includes at least three of the above four types of phthalocyanine compounds (A) to (D). That is, the near-infrared absorption filter according to the present invention includes all kinds of the four kinds of phthalocyanine compounds (A) to (D) and three kinds of phthalocyanine compounds selected from the four kinds of compounds. The selection method of the three kinds of phthalocyanine compounds, the combination of phthalocyanine compounds, the mixing ratio of each phthalocyanine compound, and the like are arbitrary. For example, in the present invention, in consideration of the specific contents of the substituents A ^{1 to} A ^{16 in} the phthalocyanine compound, the specific identification of the phthalocyanine compound thereby, particularly the infrared absorption characteristics, etc., combinations of phthalocyanine compounds, each phthalocyanine compound And the total blending amount of all phthalocyanine compounds can be determined. In addition, this invention does not exclude using together 2 or more types of compounds classified as the same kind of phthalocyanine compound. That is, for example, the case where two or more phthalocyanine compounds (A) belonging to the group of compounds classified as the phthalocyanine compound (A) are used in combination is not excluded. The same applies to the phthalocyanine compounds (B) to (D).

  In the present invention, the optical characteristics (for example, the absorption wavelength) of the near-infrared absorption filter are appropriately changed by appropriately changing the specific types and combinations of the phthalocyanine compounds, the blending amounts of the respective phthalocyanine compounds, or the blending ratios thereof. Area, light transmittance, etc.) can be arbitrarily controlled, and the most preferable near-infrared absorbing filter according to the specific use, purpose, etc. of the near-infrared absorbing filter can be provided.

Transparent Resin As the transparent resin used in the present invention, any desired purpose can be used. For example, various transparent resin materials that have been conventionally used as a display material, in particular, a display material for a plasma display can be used.

  Examples of preferred transparent resins in the present invention include (meth) acrylic resins, (meth) acrylic urethane resins, polyvinyl chloride resins, polyvinylidene chloride resins, melamine resins, urethane resins, and styrene resins. , Alkyd resins, phenolic resins, epoxy resins, polyester resins, (meth) acrylic silicone resins, alkylpolysiloxane resins, silicone resins, silicone alkyd resins, silicone urethane resins, silicone polyester resins, silicone acrylic resins Modified silicone resins such as polyvinylidene fluoride, fluoroolefin vinyl ether polymers and the like, and may be thermoplastic resins, thermosetting resins, moisture curable resins, ultraviolet curable resins, electron beam curable resins Curability such as It may be fat. In particular, those containing at least one acrylic, polyester and urethane resin component are preferred.

  Also, organic binder resins such as synthetic rubber such as ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber or natural rubber; silica sol, alkali silicate, silicon alkoxide and their (hydrolysis) Conventionally known binder resins such as inorganic binders such as condensates and phosphates may be mentioned. These may be used alone or in combination of two or more.

Other ingredients (optional ingredients)
The near-infrared absorbing film-forming composition that forms the near-infrared absorbing filter of the present invention can contain, for example, a solvent or an additive as necessary, in addition to the above-described phthalocyanine compound and transparent resin. .

  Such solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, propyl acetate, benzene, toluene, xylene, methanol, ethanol, isopropanol, chloroform, tetrahydrofuran, N, N-dimethylformamide from the viewpoint of dye solubility. , Acetonitrile, trifluoropropanol, n-hexane, n-heptane, water, and the like, but may be other than these.

  In addition, as the additive, a conventionally known additive generally used in a resin composition for forming a film, a coating film, or the like can be used. For example, a leveling agent; inorganic fine particles such as colloidal silica and alumina sol; Antifoaming agent, anti-sagging agent, silane coupling agent, titanium white, composite oxide pigment, carbon black, organic pigment, pigment intermediate and other pigments; pigment dispersant; antioxidant; viscosity modifier; Agent; Metal deactivator; Peroxide decomposing agent; Filler; Reinforcing agent; Plasticizer; Lubricant; Anticorrosive agent; Anticorrosive agent; Fluorescent brightener; Organic and inorganic UV absorber, Inorganic heat ray Absorbers; organic / inorganic flameproofing agents; antistatic agents and the like.

  In addition, although the near-infrared absorption filter by this invention contains at least 3 types in the said phthalocyanine compound (A)-(D) as an essential component, it uses further combining near-infrared absorption pigments other than these as needed. Can do.

Form of near-infrared absorption filter As a use form of the near-infrared absorption filter according to the present invention, for example, a near-infrared absorption film formed from a composition for forming a near-infrared absorption film is used as a near-infrared absorption layer on a transparent substrate. And a laminated body provided with an optical functional layer.

  FIG. 1 is a cross-sectional view illustrating a laminated structure of a near infrared absorption filter according to the present invention. The near-infrared absorption filter according to the present invention is most basically a near-infrared absorption laminate having a laminated structure in which a near-infrared absorption layer 3 is laminated on a transparent substrate 2 as indicated by reference numeral 1 in FIG. It consists of four. The transparent substrate 2 may be subjected to a treatment for improving adhesiveness that can be performed during lamination.

  The transparent substrate 2 is not particularly limited as long as a near-infrared absorbing film can be laminated as the near-infrared absorbing layer 3. For example, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cyclic polyolefin, Films made of polyolefins such as polyethylene, polypropylene and polystyrene, vinyl resins such as polyvinyl chloride and polyvinylidene chloride, polycarbonate, acrylic resin, triacetyl cellulose (TAC), polyether sulfone, or polyether ketone. These can be used alone, or the same kind or different kinds can be laminated.

  The transparency of the transparent substrate 2 is preferably such that the light transmittance in the visible region is 80% or more when the transparent substrate is a single layer. Moreover, although having transparency is preferably colorless and transparent, it is not necessarily limited to being colorless and transparent, and may be colored and transparent as long as the object of the present invention is not hindered. Good. Although the light transmittance in the visible region is preferably as high as possible, the final product requires a light transmittance of 50% or more. Is 80%, it is suitable for the purpose. Of course, as the light transmittance is higher, a plurality of transparent substrates can be laminated, so that the light transmittance of the single layer of the transparent substrate 2 is more preferably 85% or more, and most preferably 90% or more. . Reducing the thickness is also an effective means for improving the light transmittance.

  The thickness of the transparent substrate 2 is not particularly limited as long as the transparency is satisfied, but is preferably in the range of about 12 μm to about 300 μm from the viewpoint of workability. When the thickness is less than 12 μm, the transparent substrate 2 is too flexible, and stretch and wrinkles are likely to occur due to the tension during processing. In addition, if the thickness exceeds 300 μm, the flexibility of the film decreases, making it difficult to continuously wind in each step, and the processability when laminating a plurality of transparent substrates is greatly inferior. There is also.

  Examples of the method for forming the near-infrared absorbing layer 3 include: (1) applying the near-infrared absorbing film-forming composition on the transparent substrate 2, and then heating the applied near-infrared-absorbing film-forming composition to the heat; A method of forming the near-infrared absorbing layer 3 by drying or curing with ultraviolet rays, electron beams, or the like; (2) a laminate by forming a composition for forming a near-infrared absorbing film into a film and attaching it to the transparent substrate 2; The method (1) is preferable because the method (1) is simple.

  In the method for forming the near-infrared absorbing layer 3, as a method for applying the composition for forming a near-infrared absorbing film on a transparent substrate, for example, dipping, spraying, brushing, Mayer bar coating, doctor blade coating, gravure coating Various coating methods such as gravure reverse coating, kiss reverse coating, three-roll reverse coating, slit reverse die coating, die coating, or comma coating can be used.

  The thickness of the near-infrared absorbing layer 3 is not particularly limited as long as it is appropriately set depending on the intended use. For example, it is preferable to set the thickness at the time of drying to 0.5 to 1000 μm. More preferably, it is 1-100 micrometers. More preferably, it is 1-50 micrometers, Most preferably, it is 1-30 micrometers.

  Infrared-absorbing laminate 4 shown in FIG. 1 includes various layers known in the field of optical filters in addition to one or more layers in place of transparent substrate 2 or in addition to transparent substrate 2. Can be used. FIG. 2 exemplifies a laminated structure of a near-infrared absorbing filter 1B according to the present invention in which a functional layer 5 such as an electromagnetic wave shielding layer, an antireflection layer, an antifouling layer, or a neon light shielding layer is further laminated on the infrared absorbing laminate 4. FIG.

<Plasma display>
The plasma display according to the present invention is characterized in that the above-mentioned near-infrared absorbing filter is arranged on the viewing side of the display.

  When the near-infrared absorbing filter according to the present invention is used for a PDP, as shown in FIG. 3, the near-infrared absorbing filter is installed in front of the display to cut off near-infrared light emitted from the display. For this reason, if the visible light transmittance is low, the sharpness of the image is lowered. Therefore, the higher the visible light transmittance of the filter, the better. At least 30% or more, preferably 35% or more is necessary.

  The near infrared light cut region is designed to be 800 to 1000 nm where light is emitted from the PDP, and the light transmittance in that region is 30% or less.

Hereinafter, the functional layer 5 shown in FIG. 2 will be described in more detail.
Electromagnetic wave shielding layer:
The electromagnetic wave shielding layer that can be added to the near-infrared absorbing film shields electromagnetic waves generated from an electrical or electronic device, particularly a plasma display. As the electromagnetic wave shielding layer, a metal mesh layer and a transparent conductive thin film layer are used, and a metal mesh having high electromagnetic wave shielding properties is preferable. Since the metal mesh layer is formed by laminating a metal foil on a transparent substrate and forming a mesh by etching, an adhesive layer is usually interposed between the transparent substrate and the metal mesh. Adhesive layer is acrylic resin, polyester resin, polyurethane resin, polyvinyl alcohol alone or partially saponified product thereof, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, polyimide resin, epoxy resin, polyurethane ester resin It consists of adhesives such as. The metal mesh layer is not particularly limited as long as it has electromagnetic wave shielding ability. For example, copper, iron, nickel, chromium, aluminum, gold, silver, stainless steel, tungsten, chromium, Titanium or the like can be used, among which copper is preferable, and examples of the copper foil include a rolled copper foil and an electrolytic copper foil, and an electrolytic copper foil is particularly preferable. By selecting the electrolytic copper foil, the thickness can be improved to 10 μm or less, and the adhesion with chromium oxide or the like can be improved when blackened. Because it can.

  Here, in the present invention, it is preferable that one side or both sides of the metal mesh is blackened. The blackening treatment is a treatment for blackening the surface of the metal mesh with chromium oxide or the like, and when applied to the near-infrared absorbing film or a laminate thereof, the oxidation-treated surface becomes a surface on the observer side. Are arranged as follows. Since the external light on the surface of the metal mesh layer is absorbed by chromium oxide or the like formed on the surface of the metal mesh layer by this blackening treatment, it is possible to prevent light from being scattered on the surface of the metal mesh layer. .

  The aperture ratio of the metal mesh layer is preferably as low as possible from the viewpoint of electromagnetic wave shielding ability. However, since the light transmittance decreases as the aperture ratio decreases, the aperture ratio is preferably 50% or more.

  Moreover, since the opening part and the non-opening part have the unevenness | corrugation in a metal mesh layer, the planarization layer in which transparent resin was formed in the thickness more than the thickness of a metal mesh layer is laminated | stacked on the metal mesh layer. Also good.

Antifouling layer:
The anti-contamination layer that can be added to the near-infrared absorbing film or the laminate thereof, when using the near-infrared absorbing film or the laminate thereof, is caused by inadvertent contact with the surface or contamination from the environment. It is a layer formed to prevent the contaminants from adhering or to facilitate removal even if they adhere. For example, a fluorine-based coating agent, a silicon-based coating agent, a silicon / fluorine-based coating agent or the like is used, and among them, a silicon / fluorine-based coating agent is preferably applied. The thickness of these antifouling layers is preferably 100 nm or less, more preferably 10 nm or less, and even more preferably 5 nm or less. When the thickness of these antifouling layers exceeds 100 nm, the initial value of antifouling properties is excellent, but the durability is inferior. 5 nm or less is the most preferable from the balance of antifouling property and its durability.

Neon light shielding layer:
The neon light shielding layer that can be added to the near-infrared absorbing film or a laminate thereof is for cutting unnecessary light emission around 595 nm mainly emitted by excitation of neon gas in the PDP, and has an absorption maximum near this wavelength. What is necessary is just to carry out similarly to formation of the above-mentioned near-infrared absorption layer using the neon light-shielding pigment | dye and binder resin which have, and the additive etc. which are added as needed. As the neon light-shielding dye, cyanine-based, oxonol-based, methine-based, subphthalocyanine-based, or porphyrin-based compounds can be preferably used, and porphyrin-based compounds are particularly preferable in terms of durability.

Antireflection layer:
The antireflection layer that can be added to the near-infrared absorbing film or the laminate thereof is typically a laminate in which a high refractive index layer and a low refractive index layer are laminated in order, but there are also those having other laminated structures. The high refractive index layer is, for example, a thin film made of ZnO or TiO ₂ or a transparent resin film in which fine particles of these materials are dispersed. Further, the low refractive index layer, a thin film made of SiO ₂ or SiO ₂ gel film or a fluorine-containing, or a transparent resin film of fluorine and silicon-containing. Since the antireflection layer is laminated, it is possible to reduce reflection of unnecessary light such as external light on the laminated side, and to increase the contrast of the image or video of the applied display.

Antiglare layer:
Examples of the anti-glare layer that can be added to the near-infrared absorbing film or the laminate thereof include those in which beads such as polystyrene resin or acrylic resin having a diameter of about several μm are dispersed in a transparent resin. Because of this, it is intended to prevent scintillation that occurs at a specific position and direction of the display when it is placed on the front of the display.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Note that the present invention is not limited by these descriptions.

Synthesis of phthalocyanine compound (A) In a 250 ml four-necked flask, 20 g (41 mmol) of 3- (4-chlorophenoxy) -4,5-bis (phenylthio) -6-fluorophthalonitrile, 2 g of vanadium trichloride (13 Mmol), 2 g of octanol and 30 g of benzonitrile were charged and held for about 6 hours with stirring under reflux. Thereafter, 60 g of benzonitrile was added and the temperature was kept at 60 ° C., then 30 g (230 mmol) of 1- (2-aminoethyl) morpholine was added and stirred while maintaining at 60 ° C. for about 6 hours. The reaction solution was precipitated by a phthalonitrile method using a mixed solution of acetonitrile and water, and then vacuum-dried to obtain VOPc (PhS) ₈ {4-ClPhO} ₄ (OC ₄ H ₈ N (CH ₂ ) _2. 8 g of NH) ₄ was obtained (where Pc represents phthalocyanine, Ph represents phenyl, and so on). The maximum absorption wavelength when the phthalocyanine compound (a) was dispersed in a polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) was 925 nm.

Synthesis of phthalocyanine compound (B) 3- (4-chlorophenoxy) -4,5-bis (phenylthio) -6-fluorophthalonitrile instead of 3-phenoxy-4,5-bis (4-methoxyphenylthio)- VOPc {4- (CH ₃ O) PhS} ₈ (PhO) ₄ (OC ₄ H ₈ N (CH ₂ ) is the same as that of the phthalocyanine compound (A) except that 22 g (41 mmol) of 6-fluorophthalonitrile is used. 10 g of ₂ NH) ₄ was obtained. The maximum absorption wavelength when the phthalocyanine compound (B) was dispersed in a polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) was 975 nm.

Synthesis of phthalocyanine compound (C) In a 250 ml four-necked flask, 20 g (34 mmol) of 3-phenoxy-4,5-bis (2,5-dichlorophenoxy) -6-fluorophthalonitrile, 2 g of vanadium trichloride (13 Millimoles), and 30 ml of n-octanol, and the mixture was kept for about 4 hours with stirring at 170 ° C. while bubbling nitrogen. Thereafter, the mixture was cooled to room temperature, 15 g (136 mmol) of PhCH ₂ NH ₂ and 120 ml of benzonitrile were added, and the mixture was kept at 90 ° C. for about 5 hours. The reaction solution was cooled, precipitated by the phthalonitrile method, and then vacuum-dried to obtain 180 g of VOPc (2,5-Cl ₂ PhO) ₈ (PhO) ₄ (PhCH ₂ NH) ₄ . The maximum absorption wavelength when the phthalocyanine compound (C) was dispersed in a polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) was 878 nm.

Synthesis of phthalocyanine compound (D) CuPc (2,5-Cl ₂ PhO) ₈ (PhO) was carried out in the same manner as the synthesis of compound (C) except that 1 g (10 mmol) of copper chloride was used instead of vanadium trichloride. ) ₄ (PhCH ₂ NH) ₄ 180 g was obtained. The maximum absorption wavelength when the phthalocyanine compound (D) was dispersed in a polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) was 810 nm.

<Example 1>
1.1 g of the phthalocyanine compound (A), 1.9 g of the phthalocyanine compound (B), 1.6 g of the phthalocyanine compound (C), 0.83 g of the phthalocyanine compound D, a polyester resin (Byron 200, 95 g of Toyobo Co., Ltd.) and 400 g of toluene: methyl ethyl ketone (hereinafter referred to as MEK) = 1: 2 were mixed and stirred for 1 hour while being kept at 40 ° C., and the phthalocyanine compounds (A), (B), (C), (D) and Byron 200 were dissolved to produce a near infrared absorbing ink. About the mixed solvent which volatilized during the heat retention, it was added as much as the weight decreased. This solution was applied to the easy-adhesion surface of easy-adhesive PET (A4100, manufactured by Toyobo Co., Ltd.) with an applicator so that the coating weight immediately after application was 5 g / m ^2, and Dry air was applied for 2 minutes at a speed of 5 m / s and dried to obtain a near-infrared absorbing sheet.

The spectral characteristics of the obtained near-infrared absorbing sheet were measured using a spectrophotometer (manufactured by Shimadzu Corporation: UV-3100) (FIG. 4A). Moreover, when the obtained near-infrared absorbing sheet was cut into 10 cm × 10 cm and the residual solvent was measured using a gas chromatograph (GC-9A, manufactured by Shimadzu Corporation) under heating conditions of 130 ° C. for 5 minutes, toluene 20 mg / m ² and MEK 0.1 mg / m ² . When the obtained near-infrared absorbing sheet was stored under the conditions of (A) 80 ° C. × 1000 h and (B) 60 ° C. × 95% × 1000 h, almost no spectral change was observed (Condition (A): FIG. 4B, condition (b): FIG. 4C).

<Example 2>
Except not using a phthalocyanine compound (B), it carried out like Example 1 and the near-infrared absorption sheet was obtained. The sheet was measured for residual solvent in the same manner Example 1, toluene 23 mg ^/ m 2, it was MEK0.1mg / ^{m 2.} The spectral characteristics of the obtained near-infrared absorbing sheet were measured using a spectrophotometer (manufactured by Shimadzu Corporation: UV-3100) (FIG. 5 (a)), and (i) 80 ° C. × 1000h, (b) 60. When each was stored under the conditions of ° C x 95% x 1000h, almost no spectral change was observed (condition (ii): Fig. 5 (b), condition (ii): Fig. 5 (c)).

<Example 3>
As transparent resin, acrylic adhesive (SK Dyne FP-7, manufactured by Soken Chemical Co., Ltd., resin solid content = 15 wt%, solvent = ethyl acetate, MEK, etc.) 1000 g, hardener 1 (trade name) 2 g of “L-45”) and 0.5 g of curing agent 2 (trade name “E-5XM”) manufactured by the same company were mixed.

  After mixing 0.87 g of phthalocyanine compound (A), 1.5 g of phthalocyanine compound (B), 1.27 g of phthalocyanine compound (C), 0.66 g of phthalocyanine compound (D), and 146 g of MEK, The mixture was stirred for 1 hour while being kept at ° C. to prepare a MEK solution of the phthalocyanine compounds (A), (B), (C), and (D). About the MEK solvent which volatilized during the heat retention, it was added as much as the weight decreased.

The transparent resin and the MEK solution are mixed, and coated on an easy-adhesion surface of easy-adhesive PET (A4100, manufactured by Toyobo Co., Ltd.) with an applicator so that the dry weight is 20 g / m ² . Drying was performed by applying dry air at 100 ° C. for 2 minutes at a speed of 5 m / s to obtain a near-infrared absorbing sheet. The sheet was measured for residual solvent in the same manner as in Example 1, toluene 130 mg ^/ m 2, it was MEK0.2mg / ^{m 2.}

  The adhesive surface of the near-infrared absorbing sheet was adhered so that the easy-adhesive surface of easy-adhesive PET (A4100, manufactured by Toyobo Co., Ltd.) was hit. When this was stored under the conditions of 80 ° C. × 1000 h and 60 ° C. × 95% × 1000 h, almost no spectral change was observed.

<Example 4>
As a transparent resin, urethane-based dry laminating agent (A-310, manufactured by Mitsui Takeda Chemical Co., Ltd., resin solid content = 50%, solvent = ethyl acetate) was mixed with 190 g of the curing agent (A-10) manufactured by the same company. .

  After mixing 1.1 g of phthalocyanine compound (A), 1.9 g of phthalocyanine compound (B), 1.6 g of phthalocyanine compound (C), 0.83 g of phthalocyanine compound (D), and 185 g of MEK, The mixture was stirred for 1 hour while being kept at ° C. to prepare a MEK solution of phthalocyanine compounds (A), (B), (C) and (D).

The transparent resin and the MEK solution are mixed, and coated on an easy-adhesion surface of easy-adhesive PET (A4100, manufactured by Toyobo Co., Ltd.) with an applicator so that the dry weight is 10 g / m ² . Drying was performed by applying dry air at 100 ° C. for 2 minutes at a speed of 5 m / s to obtain a near-infrared absorbing sheet. The sheet was measured for residual solvent in the same manner as in Example 1, toluene 70 mg ^/ m 2, it was MEK0.1mg / ^{m 2.}

  The dry laminate surface of the near-infrared absorbing sheet was adhered so that the easy-adhesive surface of easy-adhesive PET (A4100, manufactured by Toyobo Co., Ltd.) was hit, and then cured at 45 ° C. for 4 days. The spectrum before curing was measured in the same manner as in Example 1 (FIG. 6 (a)), and the spectrum after curing was also measured in the same manner (FIG. 6 (b)). When this was stored under the conditions of 80 ° C. × 1000 h and 60 ° C. × 95% × 1000 h, almost no spectral change was observed.

<Comparative Example 1>
The same procedure as in Example 1 was conducted except that 2 g of diimmonium (IR-022, manufactured by Nippon Kayaku Co., Ltd.) was used instead of the phthalocyanine compounds (A), (B), (C), and (D). . The sheet was measured for residual solvent in the same manner as in Example 1, toluene 72 mg ^/ m 2, it was MEK0.1mg / ^{m 2.} FIG. 7A shows the spectrum before curing, and FIG. 7B shows the spectrum after curing. The spectrum changed greatly before and after curing, and deterioration of the absorption performance in the near infrared region of 800 to 1000 nm was observed.

<Comparative example 2>
The same procedure as in Example 1 was performed except that 2.3 g of only one type of phthalocyanine compound (B) was used. The sheet was measured for residual solvent in the same manner as in Example 1, toluene 22 mg ^/ m 2, it was MEK0.1mg / ^{m 2.} FIG. 8A shows the spectral characteristics of the obtained near-infrared absorbing sheet, and FIG. 8 shows the spectral characteristics after storage under the conditions of (A) 80 ° C. × 1000 h and (B) 60 ° C. × 95% × 1000 h. (B) (Condition A) and FIG. 8C (Condition B). Although almost no spectral change was observed over time, it was not possible to sufficiently cut the vicinity of 800 to 900 nm out of 800 to 1000 nm in which light emission from the PDP occurred.

<Comparative Example 3>
The same procedure as in Example 1 was performed except that 1.3 g of the phthalocyanine compound (B) and 1.2 g of the phthalocyanine compound (D) were used. The sheet was measured for residual solvent in the same manner as in Example 1, toluene 24 mg ^/ m 2, it was MEK0.1mg / ^{m 2.} FIG. 9A shows the spectral characteristics of the obtained near-infrared absorbing sheet, and FIG. 9 shows the spectral characteristics after storage under the conditions of (A) 80 ° C. × 1000 h and (B) 60 ° C. × 95% × 1000 h. (B) (Condition A) and FIG. 9C (Condition B). Although almost no spectral change was observed over time, it was not possible to sufficiently cut the vicinity of 900 nm out of 800 to 1000 nm where light was emitted from the PDP.

It is a schematic sectional drawing which shows an example of the near-infrared absorption filter of this invention. It is a schematic sectional drawing which shows the other example of the near-infrared absorption filter of this invention. It is a figure of the plasma display which has arrange | positioned the near-infrared absorption filter of this invention at the observer side. FIG. 4 shows the spectral characteristics of the near-infrared absorption filter obtained in Example 1. FIG. 4 (a) shows the initial characteristics of the filter, and FIG. 4 (b) shows the filter at 80 ° C. × FIG. 4C shows the characteristics after storing the filter under the condition of 1000 h, and FIG. 4C shows the characteristics after storing the filter under the condition of 60 ° C. × 95% × 1000 h. 5 shows the spectral characteristics of the near-infrared absorption filter obtained in Example 2. FIG. 5 (a) shows the initial characteristics of the filter, and FIG. 5 (b) shows the filter at 80 ° C. × FIG. 5C shows the characteristics after the filter was stored under the condition of 60 ° C. × 95% × 1000 h. 6 shows the spectral characteristics of the near-infrared absorption filter obtained in Example 4. FIG. 6 (a) shows the characteristics of the filter before curing, and FIG. 6 (b) shows the characteristics after curing. Is shown. 7 shows the spectral characteristics of the filter obtained in Comparative Example 1. FIG. 7 (a) shows the characteristics of the filter before curing, and FIG. 7 (b) shows the characteristics after curing. It is. 8 shows the spectral characteristics of the near-infrared absorption filter obtained in Comparative Example 2. FIG. 8 (a) shows the initial characteristics of the filter, and FIG. 8 (b) shows the filter at 80 ° C. × FIG. 8C shows the characteristics after the filter is stored under the condition of 60 ° C. × 95% × 1000 h. 9 shows the spectral characteristics of the near-infrared absorption filter obtained in Comparative Example 3. FIG. 9 (a) shows the initial characteristics of the filter, and FIG. 9 (b) shows the filter at 80 ° C. × FIG. 9C shows the characteristics after storing the filter under the condition of 1000 h, and FIG. 9C shows the characteristics after storing the filter under the condition of 60 ° C. × 95% × 1000 h.

Explanation of symbols

1, 1A, 1B Near-infrared absorbing filter 2 Transparent substrate 3 Near-infrared absorbing layer 4 Near-infrared absorbing laminate 5 Optical functional layer 6 PDP

Claims (3)

A near-infrared absorption filter for plasma display, characterized in that the transparent resin contains at least three of the following four types of phthalocyanine compounds (A) to (D).
Phthalocyanine compound (A):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are substituents via a sulfur atom, and at least three have a chlorine atom. M ¹ is oxidized) Vanadium.)
Phthalocyanine compound (B):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are substituents via a sulfur atom and substantially have no chlorine atom. M ¹ is Vanadium oxide.)
Phthalocyanine compound (C):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are a substituent via a nitrogen atom and substantially free of a substituent via a sulfur atom). M ¹ is vanadium oxide.)
Phthalocyanine compound (D):
A compound represented by the following formula [I] (provided that at least four of A ^{1 to} A ¹⁶ are a substituent via a nitrogen atom and are substantially free of a substituent via a sulfur atom. ¹ is copper.)

(In the formula [I], A ^{1 to} A ¹⁶ each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a hydroxysulfonyl group, an aminosulfonyl group, a nitrogen atom, a sulfur atom, an oxygen atom, or a halogen atom. It represents a substituent having 1 to 20 carbon atoms which may be contained, and two adjacent substituents may be connected via a linking group, and M ¹ represents vanadium oxide or copper.   The near-infrared absorption filter according to claim 1, wherein the transparent resin contains at least one or more acrylic, polyester, and urethane resin components.   A near-infrared absorption filter according to claim 1 or 2 is disposed on the viewing side of the display.

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